Journal of Environmental Sciences 19(2007) 513–522

Supercritical water oxidation for the destruction of toxic organic

wastewaters: A review
VERIANSYAH Bambang, KIM Jae-Duck ∗
Supercritical Fluid Research Laboratory, Korea Institute of Science and Technology (KIST)–Department of Green Process and System Engineering,
University of Science and Technology (UST), 39-1 Hawolgok-dong, Seoungbuk-gu, Seoul 136-791, Korea. E-mail: [email protected]

Received 16 June 2006; revised 28 September 2006; accepted 11 October 2006

Abstract
The destruction of toxic organic wastewaters from munitions demilitarization and complex industrial chemical clearly becomes an
overwhelming problem if left to conventional treatment processes. Two options, incineration and supercritical water oxidation (SCWO),
exist for the complete destruction of toxic organic wastewaters. Incinerator has associated problems such as very high cost and public
resentment; on the other hand, SCWO has proved to be a very promising method for the treatment of many different wastewaters
with extremely efficient organic waste destruction 99.99% with none of the emissions associated with incineration. In this review, the
concepts of SCWO, result and present perspectives of application, and industrial status of SCWO are critically examined and discussed.

Key words: supercritical water oxidation; toxic wastewater treatment; SCWO industrial status

Introduction land-based alternatives as land filling, deep-well injection,

and lagooning is the destruction method. Land-based dis-
The world is facing a waste crisis from organic and toxic posal does not address the ultimate destruction of toxic
wastes today. Every year the amount of those wastes gen- components of the waste and can result in the possible
erated by industrial and domestic sources increase rapidly. contamination of surrounding soil and groundwater. Deep-
The treatment of organic and toxic waste is becoming more well injection systems are subject to plugging or fouling
difficult and costly because of more stringent treatment if organic concentration of 1% or higher are allowed.
standards and discharge limitations. Public health concerns Landfills and lagoons can contribute to contamination
are the driving force for the continued legislation aimed at of the air by volatile organics. The increasing of public
providing a cleaner and safer environment. Furthermore, concern and regulatory action will restrict or prohibit land-
EPA (Environmental Protection Agency) goals suggest based disposal of many organic wastes in the future.
destruction levels up to 99.9999% of some compounds and Destruction methods based on oxidation of organic con-
use of totally enclosed treatment facilities. The increased tent for aqueous wastes include activated carbon treatment,
environmental constrains and unfavorable public opinion biological treatment, incineration, wet air oxidation, and
have challenged the continuing application of conventional supercritical oxidation. For very dilute aqueous waste
waste management techniques (Li et al., 1991). whose organic contents are less than 1%, activated carbon
Conventional technologies currently used to treat all treatment or biological treatment is often an effective de-
types of organic and toxic wastes include adsorption, struction method. In activated carbon treatment, organics
biological oxidation, chemical oxidation, land-based, and are first adsorbed onto carbon and then oxidized during
incineration. Each of these treatment methods has short- regeneration of carbon. Partially oxidized materials are
comings and therefore may not be the best option for perfectly destroyed by after-burner treatment. Main cost
treating organic and toxic wastes. Supercritical water oxi- is proportional to the organic content. So this method is
dation (SCWO) has been proposed as a technology capable not economically useful for waste containing more than
of destroying a very wide range of organic hazardous 1% organic. Biological treatment systems often become
waste. It has been drawing much attention due to effec- poisoned and cannot be sustained for many wastes with
tively destroy a large variety of high-risk wastes resulting organic concentrations of 1% or more.
from munitions demilitarization and complex industrial Incineration, on the other hand, is restricted for eco-
chemical. nomic reasons to waste streams relatively high organic
The primary advantage of the SCWO process over such concentrations. To attain high destruction efficiency for
hazardous and toxic wastes, incineration must be operated
Project supported by the Korea Institute of Science and Technology at very high temperature as 900–1100°C and often with
(KIST). *Corresponding author. E-mail: [email protected]. excess air of 100%–200%. With aqueous wastes, the
514 VERIANSYAH Bambang et al. Vol. 19

energy required to bring the water component of the waste may be intensely colored and toxic (Li et al., 1991).
to this temperature is substantial. For the aqueous wastes The above examples illustrate the utility of WAO as an
with organic content more than 25%, the heat required alternative to incineration for the treatment of dilute aque-
for high temperature can be generated from wastes. With ous wastes. However, a number of compounds, including
decreasing organic content, the supplemental fuel required m-xylene and acetic acid are refractory towards oxida-
to satisfy the energy balance becomes a major cost. Thus, tion at these conditions. Additionally, WAO often cannot
controlled incineration of aqueous waste with less than achieve the 99.9% destruction efficiencies that many newer
20% organics is the only consideration in extenuating regulations require. This motivated a look at oxidation
circumstances (Thomason and Modell, 1984). Incineration under more severe conditions, such as higher temperatures
is also being regulated to restrict stack gas emissions and pressures, which bring the reaction mixture above its
to the atmosphere. Extensive equipment must now be critical point. Thus, the supercritical oxidation process was
used downstream of the reaction system to remove NO x , born. Supercritical water oxidation, on the other hand, is
acid gasses, and particulates from the stack gases before known to attain nearly complete destruction of various
discharge. The cost of this equipment often exceeds that of organics such as PCBs, and dioxins in very short time
the incinerator itself. (Boock, 1996).
In the range of concentration of 1% to 20% organic, wet
air oxidation or SCWO is far less costly than incineration 1 Supercritical water oxidation
or active carbon treatment. Wet air oxidation (WAO) has
been offered as a method to treat wastewater, industrial Supercritical water oxidation defined as oxidation pro-
wastes, and sludge. From a public perception standpoint, cess which occurs in water above its critical point
WAO is more favorable than incineration, land application, (T c =374°C and Pc =22.1 MPa). It uses supercritical water
deep well injection, and ocean dumping because the waste as a reaction medium and exploits the unique solvat-
products can be completely converted to inert materials ing properties to provide enhanced solubility of organic
and the process can be conducted as a closed system which reactants and permanent gases (like oxygen and carbon
does not produce any hazardous byproducts. Capital costs dioxide), a single-phase environment free of inter-phase
are often higher than incineration; however, operating costs mass transfer limitations, faster reaction kinetics, and
are lower. It is possible to recover energy and inorganic an increased selectivity to complete oxidation products
in WAO. Wet air oxidation, commonly associated with (Tester et al., 1993; Savage et al., 1995; Schimeider and
sludge conditioning and some organic destruction, is a low- Abeln, 1999).
temperature process (Boock, 1996). SCWO provides a potential alternative for process-
The Zimpro-Passavant’s WAO process is typically oper- ing hazardous military wastes without the concomitant
ated in a temperature range of 150°C to 350°C and pressure production of noxious byproducts as might be experi-
range of 2–20 MPa. The operating pressure is maintained enced with combustion-based technologies (Downey et
well above the saturation pressure corresponding to the al., 1995). The process usually operates in a temperature
operating temperature so that the reaction is carried out range of 450–600°C and pressure range of 24–28 MPa.
in the liquid phase. Residence times may range from 15– It consists of the general steps shown in the block flow
120 min, and the chemical oxygen demand (COD) removal diagram in Fig.1. The aqueous waste stream containing the
may typically be approximately 75%–90%. Volatile acids organic is pressurized and preheated to reactor conditions.
constitute a substantial portion of remaining COD. The The oxidant stream, which can be an aqueous solution
formation of volatile acids, particularly acetic acid, is of hydrogen peroxide, pure oxygen, or air, is pressurized
a limitation for WAO. Furthermore, the effluent from and mixed with the organic stream. The one-phase mixture
incomplete (partial) wet oxidation of some wastewaters of water, organic and oxidant enters the reaction zone,

Fig. 1 Block flow diagram of typical SCWO process.

No. 5 Supercritical water oxidation for the destruction of toxic organic wastewaters: A review 515

where both organic compounds and oxygen are completely also been shown effective in the treatment of a highly
soluble, and the temperature is high enough that free contaminated activated sludge (Patterson et al., 2001;
radical oxidation reactions proceed rapidly. The organic Griffith and Raymond, 2002; Stendahl and Jafverstrom,
oxidizes rapidly and completely (destruction efficiency 2003), municipal sludges (Shanableh and Gloyna, 1991;
>99.99% with residence times less than one minute) to Tongdharmachart and Gloyna, 1991; Goto et al., 1997;
CO2 and H2 O (Tester et al., 1993; Savage et al., 1995; Mizuno et al., 2000), sludges from the pulp and paper
Schmieder and Abeln, 1999; Modell, 1989). industry (Modell, 1990; Modell et al., 1992, 1995), de-
If any nitrogen is present, either introduced with the inking sludge from the recycle paper industry (Gidner and
waste or if air is used as the source of O2 , the resulting Stenmark, 2002), and a combination of sludge from a pri-
product is N2 or N2 O (Killilea and Swallow, 1992). NO x mary clarifier mixed with effluent from a bleach plant and a
and SO x gases, typical undesired by-products of combus- decant of pond sludge (Cooper et al., 1997). Additionally,
tion processes, are not formed because the temperature wastes which are typically treated by a bioremediation
is too low for these oxidation pathways to be favored. process, such as urea (Timberlake et al., 1982), human
Any N2 O found can be catalytically converted to N2 . wastes (Hong et al., 1987, 1988), and waste from manned
Heteroatoms (e.g., chlorine, phosphorous, sulfur) react to space missions (Takahashi et al., 1988) are all destroyed
form their corresponding mineral acids. With the addition by SCWO.
of a suitable base, acids are neutralized and form their SCWO process has been identified as a promising
corresponding salts which precipitate out of the reacting alternative technology to incineration for the destruction
mixture allowing for their removal. It has already been of the chemical weapons stockpile (NRC, 1993). In the
proved that SCWO is an environment friendly waste US, approximately 25000 t of chemical weapons are
treatment technology that produces disposable clean liquid slated for destruction by 2006. Originally in 1982, these
(pure water), clean solid (metal oxides) and clean gases weapons were to be incinerated at each of the eight storage
(CO2 and N2 ) (Bianchetta et al., 1999; Brunner, 1994; sites in the continental USA (Umatilla Depot Activity,
Fang et al., 2000, 2005; Goto et al., 1999; Kritzer and Oregon; Tooele Army Depot, Utah; Pueblo Depot Activity,
Dinjus, 2001; Kronholm et al., 2003; Lee et al., 2004; Rice Colorado; Pine Bluff Arsenal, Arkansas; Newport Army
and Steeper, 1998; Sullivan and Tester, 2004; Veriansyah et Ammunition Plant, Indiana; Lexington Blue Grass Depot
al., 2005a, 2005b, 2005c). Activity, Kentucky; Anniston Army Depot, Alabama; and
Aberdeen Proving Ground, Maryland) and on Johnston Is-
2 Toxic organic wastes treated with supercrit- land in the Pacific (Harigel, 2000; Hogendoorn, 1997). Due
ical water oxidation to operational problems at the Johnston Island incinerator,
the increasingly poor public perception of incineration and
The SCWO process as a hazardous waste treatment the unanticipated local public opposition to building new
technology has been proven to be a viable and effective incinerators at the remaining storage locations, the Army
technique by both academia and industrial researchers. was forced to consider alternative methods for destroying
These researchers showed that SCWO indiscriminately these weapons in the early 1990’s (U.S. Congress, 1992).
and rapidly destroys a broad spectrum of organic wastes. In that report, SCWO was selected as one of four possible
SCWO has been shown effective in the treatment of toxic alternative technologies.
chlorinated chemicals such as polychlorinated biphenyls SCWO has been shown effective for destroying the
(PCBs) (Anitescu and Tavlarides, 2000, 2002, 2005; An- stockpiled chemical warfare agents (Bianchetta et al.,
itescu et al., 2004, 2005; Fang et al., 2004, 2005; Hatakeda 1999; Downey et al., 1995; Lachance et al., 1999; Snow
et al., 1997a, 1997b, 1999; Kubatova et al., 2003; O’Brien et al., 1996; Sullivan and Tester, 2004; Veriansyah et al.,
et al., 2005; Rahuman et al., 2000; Sako et al., 1999; 2005a, 2005c, 2006), propellants and energetics (Buelow,
Staszak et al., 1987; Weber et al., 2002) and the pesticide 1990, 1992; Harradine et al., 1993), and military smokes
DDT (Modell, 1990), bacteria and dioxins (Thomason et and dyes (Robinson, 1992; Rice et al., 1994). Because of
al., 1990), chlorophenol and chlorobenzene (Lin et al., the ability of SCWO to destroy broad classes of organic
1998, 1999; Lin and Wang, 1999a, 1999b, 2000a, 2000b, wastes and its ability to destroy chemical warfare agents,
2001; Muthukumaran and Gupta, 2000; Namasivayam and the three branches of USA military are building SCWO
Kavitha, 2003; Svishchev and Plugatyr, 2006) process units for their purposes. The USA Navy is developing com-
waste waters (Li et al., 1993; Sawicki and Casas, 1993; pact SCWO units for the on-board treatment of hazardous
Park et al., 2003; Portela et al., 2001a; Veriansyah et al., wastes (Kirts, 1995; Cohen et al., 1998). The USA Army
2005b), and pharmaceutical and biopharmaceutical waste commissioned Foster Wheeler Development Corporation
(Aki and Abraham, 1999; Johnston et al., 1988; Qi et in conjunction with Sandia National Laboratories and
al., 2002). Compounds which are problematic to recycle Gencorp Aerojet to build a SCWO facility at the Pine
or dispose due to the formation of hazardous by-products Bluff Arsenal in Arkansas for destroying smokes, dyes,
and residues such as the polymer polyvinylchloride and pyrotechnics (Haroldsen et al., 1996a, 1996b). The
(PVC), the flame retardant tetrabromobisphenol A, and the Army is also undergoing testing the SCWO facility built by
chlorocarbon γ-hexachlorocyclohexane and hexachloro- General Atomics in Toole, Utah for treating VX and GB.
cyclohexane, are completely oxidized without hazardous The USA Air Force awarded a contract to General Atomics
by-product formation (Hirth et al., 1998). SCWO has to design a plant for destroying solid rocket propellant
516 VERIANSYAH Bambang et al. Vol. 19

(Hurley, 1996). 3.2.2 Floating type reactor (SUWOX)

SUWOX was designed to prevent corrosion problem,
3 Supercritical water oxidation reactor sys- which was solved by dividing the construction into two
tem vessels, the pressure-resistant vessel and the inner vessel
(Casal and Schmidt, 1998). Fig.3 shows the design of the
3.1 Batch system reactor. The SCWO reaction occurs in the inner nonporous
vessel. Between those two vessels, there is a gap for small
Various batch reactors suitable for conducting SCWO
stream of water.
of organic waste are described in the literature (Calvo and
Vallejo, 2002; Goto et al., 1999; Mizuno et al., 2000;
Portela et al., 2001b; Jin et al., 2001; Lachance et al., 1999;
Thornton and Savage, 1992). This reactor usually has two
temperature zones, the upper part, to keep the reactor above
critical temperature, and the lower part, to dissolve the salt
precipitant at subcritical temperature (Kupferer, 2002).
3.2 Continuous-flow system
Organic waste treated by SCWO mostly conduct in
continuous-flow system. This is due to its flexibility for
expansion to plant or industrial scale. The type of reactor is
developed from basic tubular type to the current transpiring
wall reactor (Crooker et al., 2000; Fauvel et al.,2003, 2005;
Lee et al.,2005; Marrone et al., 2004, 2005; Wellig et al.,
2005).
3.2.1 Transpiring wall reactor (TWR)
The concept behind the TWR design includes a dual
shell consisting of an outer pressure-resistant vessel and
an inner porous vessel (Daman, 1996; Kritzer and Dinjus,
2001). Through the porous wall, supercritical water will
get through to form a thin, protecting water film. Through
this complex perspiration system, the porous liner is said
to protect the reactor against corrosion and salt deposition. Fig. 3 SUWOX reactor (Baur et al., 2005).
Fig.2 shows a simple schematic diagram of TWR. Some
group have developed a hydrothermal flame as internal Extensive study for this type of reactor was conducted
heat source in TWR (Wellig et al., 2005) and another group in Germany (Baur et al., 2005). They explore four types
have studied its application on halogenated hydrocarbons of SUWOX-base reactor for biocides treatment in SCWO.
(2,4-dichlorophenol) with 98.7% conversion at residence The destruction of organic with conversion 99.9% could be
time of 32 s., temperature of 713 K and pressure of 25 achieved, even at low oxygen supply and the shortest resi-
MPa (Lee et al., 2005). Current study and review related to dence time (1.37 min). Salt content in the effluent remained
this type of reactor is described in literature (Fauvel et al., dissolve, with concentration >200 g/L (NaCl). Another
2003, 2005; Marrone et al., 2004, 2005). group, successfully decomposed 2,4-dichlorophenol with
99.9% conversion at residence time of 34 s, temperature
of 693 K and pressure of 25 MPa (Lee et al., 2005). This
result was higher, compare to when they employed TWR
at the similar conditions.

4 Industrial status
Several reviews have summarized the current general
state of SCWO technology, as well as pilot work re-
cently performed or in progress in support of a number
of applications (Kritzer and Dinjus, 2001; NRC, 1998;
Schmieder and Abeln, 1999; Shaw and Dahmen, 2000;
Tester and Cline, 1999; Yoo et al., 2004). The promotion
of SCWO for treating industrial wastes has also met
with limited success. The main drawbacks are the high
operating pressure, possible of the reactor plugging due
Fig. 2 Transpiring wall reactor (Daman, 1996). to salt formation, corrosive behavior under certain T-P-
No. 5 Supercritical water oxidation for the destruction of toxic organic wastewaters: A review 517

xi conditions, and pre-commercial higher processing costs. also MODEC licensee. Hitachi and NGK are interested in
With active research underway to understand and resolve developing the MODEC process further for sewage sludge
the problems of plugging from salts and corrosion, the treatment (Japan Chemical Week, 1998).
development of novel reactor designs to alleviate these Both GA and Foster Wheeler have been very active in
problems and the disappearance of landfills, SCWO may recent years with several projects being conducted for three
yet become a viable waste treatment option for industrial branches of the U.S. Armed Forces. GA has demonstrated
wastes and find a nice market (Hodes et al., 2004; Kritzer successful treatment of chemical agent (HD, GB and VX)
et al., 1999; Kritzer and Dinjus, 2001; Kritzer, 2004). hydrolysate and energetics hydrolysate/secondary wastes
An even more serious problem facing SCWO having for the U.S. Army’s Assembled Chemical Weapons As-
nothing to do with the process itself is the unwillingness of sessment (ACWA) program (U.S. DOD ACWA, 1999),
industries to invest in novel, and potentially superior, waste SCWO is part of GA’s Total Solution proposed to ACWA
treatment technologies. This barrier will likely prove more for demilitarization of the complete munition (projectiles,
difficult than the technical problem facing SCWO. Regula- mortars, rockets) and associated storage and process-
tory pressure does not suffer from these constraints, and ing materials. The energetics hydrolysate/secondary waste
changes in industrial effluent discharge regulations may feeds consisted of slurry of hydrolyzed energetics (tetry-
be needed. The success of SCWO in treating the military tol, Composition B, and/or M28 propellant) along with
waste will be important for its industrial acceptance. shredded wood, plastics, and activated carbon. GA recently
Table 1 contains a list of full-scale facilities and li- completed further pilot testing for ACWA in support of a
censees of the SCWO processes developed by several full-scale design for demilitarization of chemical weapons
companies, along with recent feed material that have been stored in Pueblo, CO, and Lexington, KY (U.S. DOD
processed. MODAR, Inc., the first company to attempt to ACWA, 2002). GA also designed and tested a compact
exploit the technology commercially, performed extensive SCWO system for the U.S. Navy in 1999 for destruction
studies of destruction efficiencies for organic compound of shipboard wastes (Elliott et al., 2000). GA conducted
in the 1980’s and early 1990’s in an attempt to validate hydrolysis and SCWO testing of rocket motor propellant
the SCWO process and develop large-scale reactor system for the USA Air Force in 1995 using a 1 gpm (3.8 L/min)
for treating industrial wastes. MODAR, Inc., was acquired pilot-scale system (Defense, 1995). The Japanese compa-
by General Atomics (GA) in 1996, but GA is currently nies Komatsu, Ltd., and Kurita Water Industries, Ltd., have
only using the technology for treating military wastes. a licensing agreement with GA in commercializing SCWO
A full-scale SCWO facility based on MODAR process technology in Asia (Schmieder and Abeln, 1999).
(i.e., reverse flow, tank reactor) was constructed by Organo Foster Wheeler constructed a full-scale SCWO system
Co. by Japan in 1998 (Oe et al., 1998). In addition to based on their transpiring wall reactor design for the U.S.
having a licence to the MODAR process, organo is a li- Army’s Pine Bluff Arsenal in Arkansas in 1998 (Crooker
censee of the MODEC process (designed a SCWO reactor et al., 2000). The system was designed to treat obsolete
system capable of avoiding the salt plugging problems smoke and dye munitions at a rate of 80 lb/h (36 kg/h)
and eliminating corrosion issues for many wastes). Two of munitions. It is being operated by Sandia National
other Japanese companies, Hitachi Plant Engineering and Laboratories and has been undergoing extensive system-
Construction Co. and NGK Insulator Ltd., and a Canadian ization with surrogate feed materials since construction
firm, NORAM Engineering and Constructors, Ltd., are completion. Foster Wheeler has also conducted pilot-scale

Table 1 Commercially designed SCWO facilities currently in existence

Company Licenses Large-scale plants Application

MODAR Organo Nittetsu Semiconductor, Semiconductor manufacture wastes

Japan (constructed by Organo)
MODEC Organo, Hitachi, None Pharmaceutical wastes, pulp, and paper mill wastes,
NGK sewage sludge
General Atomics Komatsu, Kurita U.S. Army Newport Chemical Bulk VX nerve agent hydrolysate; other feed processed
Waste Industries Depot, Newport, IN in smaller-scale system; chemical agent, explosives, and
dunnage (U.S. Army), shipboard wastes (U.S. Navy),
rocket, propellant (U.S. Army Force)
Foster-Wheeler U.S. Army Pine Bluff Arsenal, Smokes and dyes; other feeds processed in smaller-
Pine Bluff, AR (operate by scale systems: chemical agent and explosives
Sandia National Laboratory) (U.S. Army), shipboard wastes (U.S. Navy)
EcoWaste Chematur Huntsman Chemical, Austin, TX Oxygenated and nitrogen-containing hydrocarbon
Technologies (EWT) (e.g., alcohols, glycols, amines)
Chematur Shinko Pantec Johnson Matthey, Brimsdown, UK Spent catalyst (recover platinum group metals and
destroy organic contaminants)
Japan (constructed by Shinko Pantec) Municipal sludge
SRI International Mitsubishi Heavy Japan PCBs, chlorinated wastes
Industries
Hydro-Processing Harlingen Wastewater Treatment Mixed municipal and industrial wastewater sludge
Plant No.2, Harlingen, TX
Hanwha Chemical Namhae Chemical Corp, Korea Wastewater from DNT/MNT Plant and Melamine Plant
518 VERIANSYAH Bambang et al. Vol. 19

testing of a transpiring wall SCWO system for the USA AHO system in Japan for PCB destruction, with plans to
Navy and Army ACWA program similar to that described build several more plants for both government and private
for GA. Testing for the Navy was performed in 1999 clients.
with halogenated solvents and photographic solution feeds HydroProcessing, LLC, has focused on the application
at 80–209 lbs/h (36–95 kg/h) (Crooker et al.,2000). The of SCWO for treating municipal wastewater sludge. Their
same system was used for ACWA testing in 2000, in patented process (Griffith et al., 1999), referred to as the
which mixtures of agent (HD, GB, VX) and energetic HydroSolidsr process, is intended to replace tradition-
(tetrytol, Composition B, M28 propellant) hydrolysates al sludge digestion and dewatering units in a standard
were processed with minimal corrosion and salt buildup wastewater treatment plant. They have operated a 0.4 gpm
in the reactor (U.S. DOD ACWA, 2001). Foster Wheeler is (1.5 L/min) tubular reactor pilot system with this feed since
part of a team who’s proposed Total Solution to ACWA for 1996, and have built a full-scale system for the Harlingen
munition demilitarization includes co-processing of agent Wastewater Treatment Plant in Harlingen, TX. The system
and energetic hydrolysates via SCWO as demonstrated. is intended to process both municipal wastewater sludge
The hydrolysate feed recipes were chosen to represent and industrial wastewater sludge from an adjacent factory
compositions expected from processing actual munitions. (Wofford and Griffith, 2001). HydroProcessing states that
Foster Wheeler recently completed further pilot testing operating costs are about 180 USD/t (dry) on (not includ-
for ACWA in 2002 in support of a full-scale design for ing any projected benefits from energy or CO2 recovery),
demilitarization of chemical weapons stored in Lexington, compared to a cost of 275 USD/t for sludge disposal by
KY. landfill or land application (Parkinson, 2001). Because of
EcoWaste Technologies (EWT) designed and built the the inherently greater amount of solids contained in the
first operating commercial SCWO plant in the USA. The sludge feed (as compared to liquid wastes), the process
plant was constructed for the Huntsman Co. (formerly incorporates a hydrocyclone after the reactor for solids
Texaco Chemical Co.) in Austin, TX, for destruction removal, and a separate patented downstream system for
of non-halogenated organic wastes produced on-site at handling pressure letdown of the solids-containing effluent
their Austin Research Laboratories. The tubular reactor stream.
system began operation in 1994. The waste feed consisted There are other companies trying to commercialize
primarily of a blend of alcohols, glycols, and amines with SCWO technology, as well. For example, Hanwha Chem-
an overall organic loading of 10 wt%, and was fed at a rate ical has constructed 2000 kg/h SCWO plant for treating
of 2425 lb/h (1100 kg/h) (McBrayer et al., 1996). DNT/MNT Plant wastewater and 35000 kg/h SCWO
Chematur Engineering (1999) acquired a licensing plant for treating Melamine Plant wastewater, which
agreement for the EWT SCWO process in Europe in 1995, were commissioned in 2000 (Hanwha Chemical, 2000).
and acquired the exclusive world-wide rights for EWT ProChemTech International, Inc. designed and built a
SCWO in 1999. SCWO is marketed by Chematur under small tubular SCWO system of 0.1 gpm (0.4 L/min) capac-
the trade name Aqua Critoxr . Chematur built a 550 lb/h ity in 1993 for treating organic-laden wastewater from a
(250 kg/h) pilot-scale SCWO system in 1998 that has since semi-conductor manufacturer (ProChemTech, 2004). No-
been tested with several mostly nitrogen-containing wastes ram Engineering and Constructors, Ltd., has recently been
(amine production wastes, non-halogenated spent cutting issued a patent (Boyd et al., 2001) on a process for
fluid, de-inking sludge, and sewage sludge) (Stenmark, utilizing SCWO for oxidation of redwater (a waste from
2001; Gidner and Stenmark, 2002). Chematur has also the manufacture of nitroaromatic explosive compounds).
constructed its first full-scale SCWO facility for Johnson Daimler Chrysler of Germany has also been interested in
Matthey in the UK (Chematur, 2001). Chematur has li- the application of SCWO for the treatment of electronic
censed the EWT SCWO process to the Shinko Pantec scrap (e.g., circuit boards) and, in collaboration with the
Co. of Japan. Under this license agreement, Shinko Pantec Fraunhofer Institute ITC, has built a mobile plant (20
has constructed an 2425 lb/h(1100 kg/h) SCWO plant for L/h) containing a tubular reactor for treating this waste
treating municipal sludge, which was commissioned in (Schmieder and Abeln, 1999).
2000.
SRI International granted its first licensing agreement of 5 Conclusions
the AHO process (i.e., carbonate-filled reactor for catalytic
oxidation and salt product adsorption) to Mitsubishi Heavy SCWO provides a potential alternative for processing
Industries (MHI) in 1999 (Waste Treatment Technology hazardous and toxic organic wastes without the con-
News, 1999). MHI has been working with SRI on com- comitant production of noxious byproduct, as might be
mercializing the AHO process since 1995, and plans to experienced with combustion based technologies. The
use it to destroy polychlorinated biphenyl (PCB) wastes primary challenges that are inhibiting the rapid commer-
at commercial facilities. Since 1998, MHI has conducted cialization of SCWO are the high operating pressure,
tests with PCBs in a pilot-scale system in Japan, demon- possible plugging of the reactor due to salt formation,
strating greater than 99.9999% destruction at 380°C and corrosive behavior, and pre-commercial higher processing
270 atm. MHI also owns a patent on the AHO process costs. With active research underway to understand and
as applied to PCB decomposition (Tateishi et al., 2000). resolve the problems of plugging from salts and corrosion,
MHI is currently designing the first full-scale commercial the development of novel reactor designs to alleviate these
No. 5 Supercritical water oxidation for the destruction of toxic organic wastewaters: A review 519

problems and the disappearance of landfills, SCWO may Water Oxidation, Gaithersburg, MD. 7.
yet become a viable waste treatment option for industrial Calvo L, Vallejo D, 2002. Formation of organic acids during
wastes and find a nice market. Given the resolution of relia- the hydrolysis and oxidation of several wastes in sub- and
bility and other engineering issues, SCWO technology has supercritical water[J]. Industrial & Engineering Chemistry
the potential to stake a claim in toxic waste management Research, 41: 6503–6509.
Casal V, Schmidt H, 1998. SUWOX–a facility for the destruction
industry and to return a sufficient profit.
of chlorinated hydrocarbons[J]. Journal of Supercritical
Acknowledgements Fluids, 13: 269–276.
Chematur A B, 1999. Company web page[EB]. http://www.
This work has been supported by the Korea Institute of chematur.se, news release dated February 18, 1999.
Science and Technology (KIST) program for supercritical Chematur A B, 2001. Company web page[EB]. http://www.
fluid research. The authors would like to thank to the Korea chematur.se, news release dated November 26, 2001.
Institute of Science and Technology, Korea. Cohen L S, Jensen D, Lee G et al., 1998. Hydrothermal oxidation
of navy excess hazardous materials[J]. Waste Management,
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